Critical loads of SO4 for surface waters in the Kola region of Russia

Precipitation falling on the Kola North of Russia is severely polluted by strong acids and heavy metals emitted from large local smelters operated by the Severonickel and Pechenganickel companies. Large areas in the affected region are considered sensitive to acid precipitation due to geological and climatological conditions. Extensive surface water acidification has taken place, particularly, in the mountain and remote tundra regions. Critical loads and their cxceedances have been calculated for 370 lakes sampled in the Kola peninsula. These data indicate that the surface waters in the Kola North are highly sensitive to acidic deposition. Using the minimum values determined for each NILU grid cell, critical loads of less than 20 meq/m²yr occur in about 50 percent of the area.     

The relationship between salmonid fish densities and critical ANC at exceeded and non-exceeded stream sites in Scotland

The critical load concept is now accepted throughout Europe as a means of estimating the sensitivity of key components of aquatic and terrestrial ecosystems to atmospheric inputs of sulphur (S) and nitrogen (N). Current UK freshwater maps, based on steady-state water chemistry, are derived using a critical acid neutralising capacity (ANC_LIM) value of zero eql^–1, which is based on the probability of occurrence of salmonid fish in lakes. In practice most acidification damage to salmonid fish occurs in nursery streams at the emergence and first feeding stages. In general a clear relationship exists between salmon (Salmo salar L.) and trout (S. trutta L.) densities in Scottish streams and ANC values. However, differences between sites depend on which ANC value is used (eg maximum, minimum or mean). By contrast, when the exceedance of critical loads is compared with salmonid densities the relationship is less clear because many exceeded sites have good salmonid densities. Many of these latter sites are found in north-west Scotland where sea-salt inputs are high and ANC is usually greater than zero eql^–1, although diatom-based studies indicated slight acidification of these waters, with a point of change in diatom flora close to ANC=20 eql^–1. These false exceedances are probably due to preferential adsorption of acidic SO₄ deposition which results in an overestimate of exceedance values. All sites with a mean ANC 0 are fishless but some sites with negative minimum ANC values had normal salmonid densities. Consequently a mean ANC_LIM value of zero in the critical load equations for UK freshwaters appears to be too low to protect salmonid stocks. Values between 20–50 eql^–1 represent a more realistic range if prevention of long term damage to salmonid stocks is to be achieved.     

Photo interpretive study of recovery of damaged lands near the metal smelters of Sudbury,Canada

Aerial photographs from 1970 and 1989 were used to assess the recovery of approximately 100000 ha of smelter-damaged lands near Sudbury, Canada. Recent improvements in air quality enabled conifers to recolonize about 22% of the semi-barrens, an area that consisted of a near monoculture of coppiced and stunted white birch (Betula papyrifera). The more heavily damaged barren areas, surrounding the three smelter sites, exhibited very little natural recovery during the study period. A municipal land reclamation program was responsible for most of the observed revegetation within the barren area. Between 1978 and 1988 approximately 2000 ha of barrens were reclaimed through soil treatment, grassing and tree planting. An estimated 7400 ha of the most heavily damaged land is still in need of immediate remedial treatment. Increased rates of natural recovery are expected in the future as SO₂ emissions are reduced. Continued municipal and expanded industrial reclamation programs in the 1990s will also greatly reduce the extent of bare land.     

Bioaccumulation of selenium by floating aquatic plants

The degree to which floating aquatic plants concentrate Se in tissues was determined for four species grown in solutions containing various levels of Se. Results of this greenhouse study showed that all four plant species, Azolla caroliniana, Eichhornia crassipes, Salvinia rotundi folia, and Lemna minor absorbed Se quickly upon exposure to Se in water as concentrated as 2.5 g Se mL^–1, and attained maximum tissue concentrations within 1 to 2 weeks. Azolla absorbed Se to the highest tissue concentration (about 1000 g Se g^–1 dry matter) from the 2.5 g Se mL^–1 solution, followed by Salvinia (700 g Se g^–1), Lemna (500 g Se g^–1),and Eichhornia (300 g Se g^–1). Plant growth appeared unaffected by solution Se concentrations lower than about 1.25 g mL^–1. These results indicate potential for rapid Se movement from water into aquatic food chains, and for use of aquatic plants for Se removal in wastewater treatment systems.     

Nitrogen critical loads for natural and semi-natural ecosystems: The empirical approach

One of the major threats to the structure and the functioning of natural and semi-natural ecosystems is the recent increase in air-borne nitrogen pollution (NH_y and NO_x). Ecological effects of increased N supply are reviewed with respect to changes in vegetation and fauna in terrestrial and aquatic natural and semi-natural ecosystems. Observed and validated changes using data of field surveys, experimental studies or, of dynamic ecosystem models (the empirical approach), are used as an indication for the impacts of N deposition. Based upon these data N critical loads are set with an indication of the reliability. Critical loads are given within a range per ecosystem, because of spatial differences in ecosystems. The following groups of ecosystems have been treated: softwater lakes, wetlands & bogs, species-rich grasslands, heathlands and forests. In this paper the effects of N deposition on softwater lakes have been discussed in detail and a summary of the N critical loads for all groups of ecosystems is presented. The nitrogen critical load for the most sensitive ecosystems (softwater lakes, ombrotrophic bogs) is between 5–10 kg N ha^–1 yr^–1, whereas a more average value for the range of studied ecosystems is 15–20 kg N ha^–1 yr^–1. Finally, major gaps in knowledge with respect to N critical loads are identified.     

Condition factor and whole-body sodium concentrations in a freshwater fish: Evidence for acidification stress and possible ionoregulatory over-compensation

Condition factor, K, was measured for 1202 blacknose dace (Rhinichthys atratulus) from three streams in Shenandoah National Park (USA) of different acid neutralizing capacities (ANCs). K is a ratio of weight standardized to length; it is an indication of the health of the individuals in a population. R. atratulus condition factor in the low-ANC stream was found to be significantly lower (11%) than that of dace measured for fish from the intermediate- and high-ANC streams. This difference, according to the results of related investigations, is likely to be biologically significant. Whole-body sodium concentrations were measured as an additional test of sublethal stress in these streams. During summer base flow conditions, mean whole-body sodium concentrations of adult R. atratulus maintained in cages were found to be highest in the low-ANC stream and lowest in the high-ANC stream. The lower condition factor of dace in the low-ANC stream may be related to whole-body sodium concentration and ion regulation. Ion regulation in the low-ANC stream may be more metabolically costly because of chronic sublethal pH stress. R. atratulus may maintain high body Na⁺ concentrations in low ANC- and ionic strength waters in order to provide a buffer against large episodic pH depressions. The metabolic cost of this ionoregulatory over-compensation may necessitate the diversion of energy from somatic growth and explain the poorer condition of fish from such waters.     

Nutritional stress in ficea sitchensis plantations in coastal British columbia: The effects of gaultheria shallon and declining site fertility

Examples of nutritional stress in conifer seedlings caused by competing ericaceous species (e.g. Calluna and Kalmia), have been reported in several parts of the world. Nutritional stress (primarily N deficiency) has been reported in Sitka spruce (Picea sitchensis) plantations growing in association with an ericaceous species, salal (Gaultheria shallon), in coastal British Columbia. Nutritional interference by salal was investigated on a chronosequence of sites up to 10 yr after clearcutting and slashburning. No direct evidence for an allelopathic contribution to the N stress was obtained. However, the rapid accumulation of salal fine roots and rhizomes, and the nutrients contained therein, provides a partial explanation for the observed stress symptoms. Soil analyses and seedling bioassays demonstrated a reduction in fertility in the period 8 to 10 yr after clearcutting and slashburning in comparison to the period 2 to 4 yr, which is believed to impose further nutritional stress on Sitka spruce. It is concluded that the nutritional stress in these Sitka spruce plantations is caused by a combination of (1) salal competition for nutrients and their subsequent immobilization in salal biomass, and (2) declining site fertility caused by the termination of the flush of nutrients (the assert period) that occurs in the immediate post-clearcutting and slashburning period. Sustaining good growth of plantations under such circumstances will require site nutrient management as well as vegetation management.     

Relation between sulphur concentrations in the Scots pine needles and the air in northernmost Europe

The SO₂ emissions from the Kola Peninsula in Arctic Russia (totalling around 600 Gg(SO₂) yr^–1 at the beginning of the 1990s) produce an atmospheric SO₂ concentration gradient to the northernmost Europe. This gradient covers the range from >50 g m^–3 in the vicinity of the sources to 1 g m^–3 in Finnish Lapland. In the present study, the measured sulphur concentrations in Scots pine needles were compared with the estimated distribution of atmospheric SO₂. The total sulphur concentrations in the needles ranged from 741 to 2017 mg kg^–1. Strongly elevated concentrations (> 1200 mg kg^–1) were found within 40 km from the smelters corresponding to an area where the annual mean atmospheric SO₂ concentration exceeded 10 g m^–3. The foliar sulphur concentrations (total, organic and inorganic) show a high correlation with the estimated mean SO₂ concentration distribution in the air. Consequently the foliar sulphur concentrations reflected the atmospheric sulphur load well. The data presented here show that uptake via stomata is an important deposition pathway also in the arctic conditions with a short growing season.     

Sulphur isotope characteristics of two north Bohemian forest catchments

Sulphate concentrations and ³⁴S ratios were monitored in bulk precipitation, spruce throughfall, and soil water (depth of 30 and 90 cm) at ervená jáma (CER) and Naetín (NAC), two severely polluted sites in the Czech Republic, between December 1992 and September 1994. Throughfall [SO₄ ^2–], up to 80 mg L^–1 in winter and as low as 7 mg L^–1 in summer, was higher than [SO₄ ^2–] in bulk precipitation (annual average 6 mg L^–1). There was a distinct seasonaity in S isotope abundances, with lower ³⁴S_BULK in summer (+4 per mil CER, + 6 per mil NAC) and lower ³⁴S_TF in winter (+3 per mil CER, +4 per mil NAC). Wintertime ³⁴S_BULK was around +8 per mil at CER and +10 per mil at NAC, summertime ³⁴S_TF was close to +7 per mil at both sites. For only a 1- month period in spring, bulk precipitation S became isotopically lighter than throughfall S. Bulk precipitation data from CER were in good agreement with those from the nearby monitoring station Lesná (LES), typically differing by less than 10 mg L^–1 and 2 per mil in [SO₄ ^2–] and ³⁴S, respectively. Suction lysimeters (soil depth of 30 and 90 cm) yielded higher sulphate concentrations and lower ³⁴S ratios compared to both bulk and throughfall precipitation. Little seasonality was observed in [SO₄ ^2–] at 30 cm (around 40 mg L^–1); at 90 cm [SO₄ ^2–] was higher in winter (70 mg L^–1) than in summer (45 mg L^–1). ³⁴S at 90 cm was <+5 per=" mil=" in=" 1993=" and=" up=" to=" +7.5=" in=" 1994,=" lower=" in=" the=" first=" year=" and=" higher=" in=" the=" second=" year=" compared=" to=" the=" depth=" of=" 30=" cm.=" sulphur=" fluxes=" at=" cer=" and=" nac=" are=" characterized=" by=" distinct=" isotope=" compositions=" and=" can=" therefore=" be=" used=" to=" trace=" s=" pathways=" and=" transformations=" in=" the=" forest=">     

Acid precipitation and its influence upon aquatic ecosystems — An overview

The impact of acid precipitation reflects a usually deleterious balance between good and bad effects which may lead to serious and sometimes extreme degradation of aquatic as well as terrestrial ecosystems, particularly around metal smelters. Addition of H ions as H₂SO₄, HNO₃, and HCl can alter and impoverish the species composition of biotic communities, and lead to severe leaching of beneficial metal cations such as Ca from ecosystems. Heavy metals and other trace elements which accompany acid precipitation may reach toxic levels, particularly where acid fallout leaches additional amounts from the soil into streams and lakes. Complex and often toxic hydrocarbons also comprise a little known organic component of acid precipitation. Alternatively, acid precipitation usually is enriched in plant nutrients such as nitrate- and ammonia-nitrogen, K, Ca, and S; and at certain concentrations some of the associated trace elements may also be beneficial. Moreover the initial effect of soil leaching by acid fallout may be to enrich aquatic ecosystems in metal cations such as Ca. Basic materials in air pollution, biogenic NH₃ from the soil, dust fall from arid regions, and soils rich in adsorbed metal cations or in carbonates may neutralize some of the harmful effects of acid precipitation upon ecosystems. However, associated heavy metals, other trace elements, and toxic hydrocarbons may still constitute serious problems in many environments.     

Nitrex: The timing of response of coniferous forest ecosystems to experimentally-changed nitrogen deposition

In large regions of Europe and eastern North America atmospheric deposition of inorganic nitrogen (N) compounds has greatly increased the natural external supply to forest ecosystems. This leads to N saturation, in which availability of inorganic N is in excess of biological demand and the ecosystem is unable to retain all incoming N. The large-scale experiments of the NITREX project (NITRogen saturation EXperiments) are designed to provide information regarding the patterns and rates of responses of coniferous forest ecosystems to increases in N deposition and the reversibility and recovery of impacted ecosystems following reductions in N deposition.The timing of ecosystem response generally followed a hypothesized cascade of response. In all sites N outputs have responded markedly but to very different degrees within the first three years of treatment. Within this time significant effects on soil processes and on vegetation have only been detected at two sites. This delayed response is explained by the large capacity of the soil system to buffer the increased N supply by microbial immobilization and adsorption. We believe that this concept provides a framework for the evaluation and prediction of the ecosystem response to environmental change.     

The “shenandoah national park: Fish in sensitive habitats” (SNP: FISH) project. An integrated assessment of fish community responses to stream acidification

The Shenandoah National Park: Fish in Sensitive Habitats (SNP:FISH) project is a response to declining pH and acid neutralizing capacity in Shenandoah National Park (SNP) streams. SNP receives more atmospheric sulfate than any other USA national park, and pH had decreased to the point where early negative effects on fish were expected. SNP provides the opportunity to study the early stages of acidification effects on fish. Three different classes of geological formations yield streams with low-ANC (0 Eq/L), intermediate-ANC (60–100 Eq/L) or high-ANC (150–200 Eq/L) waters in SNP. This allows a comparison of responses across a water quality gradient in a small geographic area receiving similar deposition. Both chronic and episodic acidification occur in SNP streams. Biological effects are apparent in fish species richness, population density, condition factor, age, size, and bioassay survival. A primary project objective was to provide the necessary data for development and testing models for forecasting changes in fish communities resulting from changes in stream chemistry. Monitored variables include several which are predictive of acidification effects on SNP fish communities.     

Contribution of zooplankton to the total cadmium pool in Canadian shield lakes varying in acidity

Crustacean zooplankton >250 m in size contributed 0.002 to 11% (median of 1.3%) of the total Cd in the epilimnia of 39 Canadian Shield lakes that ranged in pH from 4.7 to 8.3. The contribution of zooplankton to the total Cd pool was consistently low (1%) only in clear water lakes with pH < 5.0.=" in=" three=" intensively=" studied=" lakes,=" the=" contribution=" of=" zooplankton=" to=" total=" aqueous=" cd=" varied=" with=" time=" and=" depth,=" the=" maximum=" contribution=" (4=" to=" 6%)=" occurring=" in=" the=" metalimnion=" in=" mid-summer.=" changes=" with=" depth=" and=" time=" were=" principally=" a=" product=" of=" seasonal=" changes=" in=" zooplankton=" biomass=" and=" seasonal=" succession=" of=" species=" with=" inherently=" different=" tendencies=" to=" accumulate=" cd.=" implications=" for=" the=" study=" of=" cd=" cycling=" in=" lakes=" are=">     

Acidic deposition,ecosystem processes,and nitrogen saturation in a high elevation Southern Appalachian watershed

High-elevation red spruce-Fraser fir forests in the Southern Appalachian mountains: 1) receive among the highest rates of atmospheric deposition measured in North America, 2) contain old-growth forests, 3) have shown declines in forest health, 4) have sustained high insect-caused fir mortality, and 5) contain poorly buffered soils and stream systems. High rates of nitrogen and sulphur deposition (1900 and 2200 Eq·ha^–1·yr^–1, respectively) are dominated by dry and cloud deposition processes. Large leaching fluxes of nitrate-nitrogen (100–1400 Eq·ha^–1·yr^–1) occur within the soil profile. We have expanded the study to the watershed scale with monitoring of: precipitation, throughfall, stream hydrology, and stream chemistry. Two streamlets drain the 17.4 ha Noland Divide Watershed (1676–1920m) located in the Great Smoky Mountains National Park. A network of 50 20x20 m plots is being used to assess stand structure, biomass, and soil nutrient pools. Nitrate is the predominant anion in the streamlets (weighted concentrations: 47 and 54 eq·L^–1 NO₃ ^–; 31 and 43 eq·L^–1 SO₄ ^2–). Watershed nitrate export is extremely high (1000 Eq·ha^–1 yr^–1), facilitating significant base cation exports. Stream acid neutralizing capacity values are extremely low (–10 to 20 eq·L^–1) and episodic acidifications (pH declines of a full unit in days or weeks time) occur. Annual streamwater sulfate export is on the order of 770 Eq·ha^–1yr^–1 or about one-third of total annual inputs, indicating there is net watershed sulfate retention. The system is highly nitrogen saturated (Stage 2, Stoddard, 1994) and this condition promotes both chronic and episodic stream acidification.     

The toxic mixing zone of neutral and acidic river water: Acute aluminium toxicity in brown trout (Salmo trutta L.)

Mixing of acid river water containing aluminium (pH 5.1, Al 345 g.l^–1) with neutral water of a lake (pH 7.0, Al 73 g.l^–1) resulted in water (pH 6.4, Al 245 g.l^–1) with a pH (6.4) and Al concentration (245 g.l^–1) expected to have low toxicity to fish on the basis of current Al toxicity models. However, under semi-field conditions the freshly mixed water (a few sec. after mixing) proved to be highly toxic to brown trout. The fish were exposed to the water at different places along a 30 m channel. At the beginning of the channel acid and neutral water were continuously mixed; the mixed water left the channel after 340 sec. The cells of the gills showed a highly increased rate of cell death by apoptosis and necrosis. Intercellular spaces were enlarged, and many leucocytes penetrated in these spaces. Mucus release was stimulated to depletion. Plasma chloride levels were hardly affected. There was a clear gradient in the deleterious effects on the fish along the channel. The fish at the beginning of the channel (about 12 sec. after mixing of the water), were severely affected, whereas the fish kept at the end of the channel (340 sec. after mixing) were only mildly affected. In the natural situation fish will relatively quickly pass through a mixing zone. In our study we therefore focused on the effects on fish after a 60 min exposure to a mixing zone (5 sec after mixing), with subsequent recovery in a region downstream of the confluence and in neutral water with low Al. The recovery in the downstream area (at the end of the channel, i.e. 5 min after mixing) was clearly hampered when compared to the recovery in neutral water with low aluminium. Thus, a short exposure to the toxic mixing zone followed by a stay in water downstream of this zone, as may occur in nature, is detrimental to migrating trout. We conclude that freshly mixed acid and neutral water contain toxic components during the first seconds to minutes after mixing, that can not be explained by current models on aluminium toxicity.     

Biogeochemistry of aluminum in a forest catchment in the Czech Republic impacted by atmospheric inputs of strong acids

The Lysina catchment in the Czech Republic was studied to investigate the biogeochemical response of Al to high loadings of acidic deposition. The catchment supports Norway spruce plantations and is underlain by granite and podzolic soil. Atmospheric deposition to the site was characterized by high H⁺ and SO₄ ^2– fluxes in throughfall. The volume-weighted average concentration of total Al (Al_t) was 28 mol L^–1 in the O horizon soil solution. About 50% of Al_t in the O horizon was in the form of potentially-toxic inorganic monomeric Al (Al_i). In the E horizon, Al_t increased to 71 mol L^–1, and Al_i comprised 80% of Al_t. The concentration of Al_t (120 mol L^–1) and the fraction of Al_i (85%) increased in the lower mineral soil due to increases in Al_i and decreases in organic monomeric Al (Al_o). Shallow ground water was less acidic and had lower Al_t concentration (29 mol L^–1). The volume-weighted average concentration of Al_t was extremely high in stream water (60 mol L^–1) with Al_i accounting for about 60% of Al_t. The major species of Al_i in stream water were fluorocomplexes (Al-F) and aquo Al³⁺. Soil solutions in the root zone were undersaturated with respect to all Al-bearing mineral phases. However, stream water exhibited Al_i concentrations close to solubility with jurbanite. Acidic waters and elevated Al concentrations reflected the limited supply of basic cations on the soil exchange complex and slow weathering, which was unable to neutralize atmospheric inputs of strong acids.     

Ionic composition of rainwater and atmospheric aerosols in Sardinia,southern Mediterranean

The ionic composition of 55 aerosol samples and 31 precipitation events collected in a coastal site in southern Sardinia (Capo Carbonara, 39°06 N; 09°31 E) were compared. The samples were collected during one year period (Oct'90/Oct'91) and showed high variability in composition according to meteorological conditions. Rain and soluble part of aerosol showed a strikingly similar ionic composition: most significant anions were chlorine and sulphate, and sodium is the principal cations, followed by magnesium and calcium. The acid events are associated with N-NW trajectories (anthropogenic influxes from N. Europe) with avg. pH=4.65, non sea salt (nss) Ca=60 eq/l and NO₃/_nssSO₄=0.6. Southern precipitations are influenced by Saharan dust alkaline effects, with avg. pH=6.75,_nssCa=271 eq/l and NO₃/_nssSO₄=0.4. Na/Cl ratio in rain is similar to sea water (0.87), whilst in aerosols there is a Cl loss (Na/Cl=1.10), probably due to reaction with nitric acid. Total fluxes of Ca, Mg, NO₃ and SO₄ were 104, 9, 64 and 113 g/cm², and wet deposition exceeded (65–90%) dry deposition. Scavenging ratios (SR) as defined by the equation:SR=[(Ci)rain/(Ci)air] ^*d, (d=1200g/m³) were calculated, using geometric means (Ci) of precipitation and aerosols collected concurrently during the period (a total of 23 samples). The SR values are Ca=3400, Cl=2400, Na, K, SO₄=1700, Mg=1000 and NO₃=750. These numbers could be useful to infer total fluxes by using simply rainwater ionic composition in Mediterranean semi-arid sites like Sardinia.     

Perch mercury content is related to acidity and color of 26 Russian lakes

We determined mercury in fish (perch Perca fluviatilis) from 26 Russian lakes in three regions over four years. The lakes ranged in size from 2 to 395,000 ha, in pH from 4.5 to 10.0, and in color from 3 to 190 hazen. Sixteen lakes were drainage lakes, with permanent outlets, and 10 were seepage lakes, with no permanent inlets or outlets. The lakes were generally located in forested regions with little or no human habitation in the watershed. The three regions were geologically distinct: Precambrian Shield granitic bedrock covered with thin soil; Triassic bedrock covered with thick glacial tills; and Triassic bedrock covered with thin sediments. At each lake water samples were collected and analyzed for pH, add neutralizing capacity (ANC), major cations, and anions. Dissolved mercury species were estimated with a thermodynamic equilibrium model (MINTEQA2). Mercury content of dorsal muscle varied from 0.04 to 1.0 g/g wet weight, and was linearly related to calculated HgCH₃Cl (r²0.68, p<0.001). lake=">₃Cl, in turn, was related to lake pH (r²=0.86, p<0.001). stepwise=" multiple=" regression=" selected=" lake=">₃Cl and color as the factors most highly related to fish mercury content, with the model accounting for 75% of the variation.